Biocide Compositions Comprising Alkoxylated Oligoglycerol Esters

ABSTRACT

Suggested are biocide compositions, comprising (a) Alkoxylated oligoglycerol esters; (b) Biocides and optionally (c) Oil components or co-solvents and/or (d) Emulsifiers. The compositions show excellent adjuvant properties.

FIELD OF THE INVENTION

The present invention relates to the area of agrochemicals and refers tobiocide compositions comprising alkoxylated oligoglycerol esters andtheir use as adjuvants for biocides.

BACKGROUND OF THE INVENTION

Biocides, and in particular pesticides such as fungicides, insecticidesand herbicides, are important auxiliary agents for agriculture in orderto protect crops and to increase their quality and harvest yield.Depending on the various and often very specific needs, a magnitude ofactives exists showing very different chemical structures andbehaviours. Nevertheless, it is well known from the state of the artthat it remains difficult to prepare liquid compositions of theseactives which are exhibiting a satisfying stability, especially ifstored at very low or elevated temperatures over a longer period. Inaddition to storage stability and the ability to prepare stable tankmixes, the influence of additives and adjuvants on bioperformance is ofelevated importance. Their choice is governed by many additionalparameters, such as ease to manufacture, a low toxicological andeco-toxicological profile, their compatibility such formulations such asemulsifiable concentrates (EC), oil in water emulsions (EW),suspo-emulsions (SE) and concentrated suspensions in water (SC) or inoil (OD)

Ethoxylated polyol esters are known as additives and adjuvants inagrochemical applications for a long time. For example DD 268147 A1describes the use of ethoxylated soy bean oil as an adjuvant forherbicides, especially bromoxynil potassium salt. WO 96/022109 A1(SEPPIC) claims a group of ethoxylated polyol esters as ingredients forpesticide and pharmaceutical formulations. Finally, EP 0539980 B1 and EP0765602 B1, both assigned to Kao, disclose di- and oligoglycerol estersin combination with other nonionic surfactants as adjuvants inparticular for herbicides and plant growth promoters. However, none ofthese adjuvants exhibit over a broad spectrum of different biocides asatisfying performance.

Therefore, the problem underlying the present invention has been toovercome the disadvantages of the state of the art. In particular it hasbeen the object to provide new additives for agricultural compositionscombining superior adjuvant properties in order to support and increasethe performance of various biocides and high stability of thecompositions also over longer storage times and different storagetemperatures.

DETAILED DESCRIPTION OF THE INVENTION

The present invention refers to biocide compositions, comprising

(a) Alkoxylated oligoglycerol esters,(b) Biocides and optionally(c) Oil components and/or co-solvents and/or

(d) Emulsifiers.

Surprisingly it has been observed that alkoxylated oligoglycerol esters,and in particular ethoxylated diglycerol esters based on unsaturatedfatty acids exhibiting superior adjuvant performance compared to similarnon-alkoxylated compounds The products improve the weed controlproperties of many aqueous biocide formulations, especially of wellknown biocides like for example glyphosate or epoxiconazole.Compositions comprising alkoxylated oligoglycerol esters according tothe present invention also exhibit better storage stability whencompared especially with tallow amine ethoxylates.

Alkoxylated Oligoglycerol Esters

Oligolycerol esters and their alkoxylation products represent well knownnon-ionic surfactants obtainable according to standard procedures oforganic chemistry, for example by direct esterification ortransesterification of the related alkoxylated oligoglycerol with fattyacids or fatty acid methyl esters. Alkoxylated oligoglycerol estersforming compound (a) of the present invention typically follow generalformula (I)

in which R¹, R² and R³ independently represent either hydrogen or asaturated or unsaturated, linear or branched and optionally hydroxysubstituted acyl radical having 2 to 22, preferably 6 to 22 and morepreferably 16 to 18 carbon atoms and up to three double bonds oncondition that at least one of the groups R¹, R² and R³ is differentfrom hydrogen, AO stands for an alkylene oxide unit selected fromethylene oxide, propylene oxide, butylene oxide and their mixtures, n1,n2 and n3 independently mean integers in the range from 1 to about 100on condition that the sum (n1+n2+n3) is an integer in the range of about10 to about 200, and x means an integer in the range of 1.1 to 10.

As formula (I) shows, the alkoxylated oligoglycerol esters cover a widerange of species, since the molecule can be tailored by modifying one ormore of the following structural features:

-   -   Degree of oligomerisation of the glycerol backbone;    -   Type and degree of alkoxylation;    -   Type of fatty acid moiety and    -   Degree of esterification.

Oligoglycerol in the context of the present invention means oligomers ofglycerol obtainable for example by alkaline condensation of glycerolunder high temperature conditions or polycondensation of epichlorhydrin.The oligomers may be either linear or branched or even cyclic. Theaverage degree of oligomerisation is between 1.1 and 10, preferably 1.5and 5 and more preferably between 2 and 4. For clarity reasons it shouldbe noted that the degree of oligomerisation represents an average value.For example a degree of oligomerisation of 1.1 means that a mixture wasobtained comprising about 90% unreacted glycerol and 10% higheroligomers, in particular diglycerol. Diglycerol esters according to thepresent invention typically comprise either about 90% diglycerol estersand 10% higher oligomers or a raw mixture of oligomerised glycerol withdegree of polymerization between 1 and 6, preferably an average of 2.

As far as the alkylene oxide units are concerned it is stated that onemay apply ethoxylates, propoxylates, butoxylates or their mixtures. Thepolyalkylene glycol chain may comprise these units blockwise or inrandom distribution. It is possible that the oligoglycerol estersaccording to the present invention contain up to 200 alkylene oxideunits. The preferred species, however, contain between 5 and 50 and moreparticularly between 10 and 15 alkylene oxide units, preferably ethyleneoxide units.

The fatty acids forming the lipophilic part of the molecule can bederived from short chain carboxylic acids or medium or long chain fattyacids, such as acetic acid, propionic acid, butyric acid, capric acid,caprylic acid, capronic acid, lauric acid, myristic acid, palmitic acid,stearic acid, 12-hydroxy stearic acid, isostearic acid, behenic acid andtheir mixtures. Preferred, however, are unsaturated fatty acids as forexample oleic acid, elaidinic acid, linolic acid, linoleic acid,conjugated linoleic acid, ricinoleic acid and their mixtures includingtechnical grade fatty acid mixtures obtained for example from sunfloweroil, high-oleic sunflower oil (HOSO), line seed oil, olive oil and thelike.

The alkoxylated oligoglycerol esters may be fully esterified or in part.Preferred are species showing a degree of esterification between 1 and3, in particular of about 2. It should be understood that also thedegree of esterification represents an average value. In particularpreferred species according to the present invention represent either

-   -   Diglycerol esters;    -   Ethoxylated oligoglycerol esters, or    -   Alkoxylate oligoglycerol esters derived from saturated and        unsaturated fatty acids.

Particularly preferred are of course those species combining all threefeatures which means ethoxylated diglycerol esters derived fromsaturated and unsaturated fatty acids.

Biocides

A biocide, also called bio-active agent (component b) in the context ofthe present invention is a plant protection agent, more particular achemical substance capable of killing different forms of livingorganisms used in fields such as medicine, agriculture, forestry, andmosquito control. Also counted under the group of biocides are so-calledplant growth regulators. Usually, biocides are divided into twosub-groups:

-   -   pesticides, which includes fungicides, herbicides, insecticides,        algicides, moluscicides, miticides and rodenticides, (here, The        Pesticide Manual, 14^(th) edition, BCPC 2006 is included as a        reference, it provides information about the individual mode of        actions of active ingredients) and    -   antimicrobials, which includes germicides, antibiotics,        antibacterials, antivirals, antifungals, antiprotozoals and        antiparasites.

Biocides can also be added to other materials (typically liquids) toprotect the material from biological infestation and growth. Forexample, certain types of quaternary ammonium compounds (quats) can beadded to pool water or industrial water systems to act as an algicide,protecting the water from infestation and growth of algae.

a) Pesticides

The U.S Environmental Protection Agency (EPA) defines a pesticide as“any substance or mixture of substances intended for preventing,destroying, repelling, or mitigating any pest”. A pesticide may be achemical substance or biological agent (such as a virus or bacteria)used against pests including insects, plant pathogens, weeds, mollusks,birds, mammals, fish, nematodes (roundworms) and microbes that competewith humans for food, destroy property, spread disease or are anuisance. In the following examples, pesticides suitable for theagrochemical compositions according to the present invention are given:

b) Fungicides

A fungicide is one of three main methods of pest control—the chemicalcontrol of fungi in this case. Fungicides are chemical compounds used toprevent the spread of fungi in gardens and crops. Fungicides are alsoused to fight fungal infections. Fungicides can either be contact orsystemic. A contact fungicide kills fungi when sprayed on its surface. Asystemic fungicide has to be absorbed by the fungus before the fungusdies. Examples for suitable fungicides, according to the presentinvention, encompass the following chemical classes and correspondingexamples:

-   -   Aminopyrimidines such as bupirimate,    -   Anilinopyrimidines such as cyprodinil, mepanipyrim,        pyrimethanil,    -   Heteroaromatics such as hymexazol,    -   Heteroaromatic hydrocarbons such as etridiazole,    -   Chlorophenyls/Nitroanilines such as chloroneb, dicloran,        quintozene, tecnazene, tolclofos-methyl,    -   Benzamide fungicides such as zoxamide,    -   Benzenesulfonamides such as flusulfamide,    -   Benzimidazoles such as acibenzolar, benomyl, benzothiazole,        carbendazim, fuberidazole, metrafenone, probenazole,        thiabendazole, triazoxide, and benzimidazole precursor        fungicides,    -   Carbamates such as propamocarb, diethofencarb,    -   Carboxamides such as boscalid, diclocymet, ethaboxam,        flutolanil, penthiopyrad, thifluzamide    -   Chloronitriles such chlorothalonil,    -   Cinnamic acid amides such as dimethomorph, flumorph,    -   Cyanoacetamide oximes such as cymoxanil,    -   Cyclopropancarboxamides such as carpropamid,    -   Dicarboximides such as iprodione, octhilinone, procymidone,        vinclozolin    -   Dimethyldithiocarbamates such ferbam, metam, thiram, ziram,    -   Dinitroanilines such as fluazinam,    -   Dithiocarbamates such as mancopper, mancozeb, maneb, metiram,        nabam, propineb, zineb,    -   Dithiolanes such as isoprothiolane,    -   Glucopyranosyl antibiotics such as streptomycin, validamycin,    -   Guanidines such as dodine, guazatine, iminoctadine,    -   Hexopyranosyl antibiotics such as kasugamycin,    -   Hydroxyanilides such as fenhexamid,    -   Imidazoles such as imazalil, oxpoconazole, pefurazoate,        prochloraz, triflumizole,    -   Imidazolinones such as fenamidone,    -   Inorganics such as Bordeaux mixture, copper hydroxide, copper        naphthenate, copper oleate, copper oxychloride, copper(II)        sulfate, copper sulfate, copper(II) acetate, copper(II)        carbonate, cuprous oxide, sulfur,    -   Isobenzofuranones such as phthalide,    -   Mandelamides such as mandipropamide,    -   Morpholines such as dodemorph, fenpropimorph, tridemorph,        fenpropidin, piperalin, spiroxamine, aldimorph    -   Organotins such as fentin,    -   Oxazolidinones such as oxadixyl,    -   Phenylamides such as benalaxyl, benalaxyl-M, furalaxyl,        metalaxyl, metalaxyl-M, ofurace,    -   Phenylpyrazoles such as fipronil,    -   Phenylpyrroles such as fludioxonil,    -   Phenylureas such as pencycuron,    -   Phosphonates such fosetyl,    -   Phthalamic acids such as tecloftalam,    -   Phthalimides such as captafol, captan, folpet,    -   Piperazines such as triforine,    -   Propionamides such as fenoxanil,    -   Pyridines such as pyrifenox,    -   Pyrimidines such as fenarimol, nuarimol,    -   Pyrroloquinolinones such as pyroquilon,    -   Qils such as cyazofamid,    -   Quinazolinones such as proquinazid,    -   Quinolines such as quinoxyfen,    -   Quinones such as dithianon,    -   Sulfamides such as tolylfluanid, dichlofluanid,    -   Strobilurines such as azoxystrobin, dimoxystrobin, famoxadone,        fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin,        pyraclostrobin, trifloxystrobin, orysastrobin,    -   Thiocarbamates such as methasulfocarb,    -   Thiophanates such as thiophanate-methyl,    -   Thiophencarboxamides such silthiofam,    -   Triazole fungicides such as azaconazole, bitertanol,        bromuconazole, cyproconazole, difenoconazole, diniconazole,        epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,        flutriafol, fluotrimazole, hexaconazole, imibenconazole,        ipconazole, metconazole, myclobutanil, penconazole,        propiconazole, prothioconazole, simeconazole, tebuconazole,        tetraconazole, triadimefon, triadimenol, triticonazole,        quinconazole    -   Triazolobenzothidazoles such as tricyclazole,    -   Valinamide carbamates such as iprovalicarb, benthiavalicarb    -   Fluopicolide    -   Pentachlorophenol        and their mixtures.

c) Herbicides

An herbicide is a pesticide used to kill unwanted plants. Selectiveherbicides kill specific targets while leaving the desired croprelatively unharmed. Some of these act by interfering with the growth ofthe weed and are often based on plant hormones. Herbicides used to clearwaste ground are nonselective and kill all plant material with whichthey come into contact. Herbicides are widely used in agriculture and inlandscape turf management. They are applied in total vegetation control(TVC) programs for maintenance of highways and railroads. Smallerquantities are used in forestry, pasture systems, and management ofareas set aside as wildlife habitat. In general, active ingredientsrepresenting including various chemical classes and correspondingexamples can be used

-   -   Anilides such as propanil    -   Aryloxycarboxylic acids e.g. MCPA-thioethyl    -   Aryloxyphenoxypropionates e.g. clodinafop-propargyl,        cyhalofop-butyl, diclofops, fluazifops, haloxyfops, quizalofops,    -   Chloroacetamides e.g. acetolochlor, alachlor, butachlor,        dimethenamid, metolachlor, propachlor    -   Cyclohexanedione oximes e.g. clethodim, sethoxydim, tralkoxydim,    -   Benzamides such as isoxaben    -   Benzimidazoles such as dicamba, ethofumesate    -   Dinitroanilines e.g. trifluralin, pendimethalin,    -   Diphenyl ethers e.g. aclonifen, oxyfluorfen,    -   The glycine derivative glyphosate, a systemic nonselective (it        kills any type of plant) herbicide used in no-till burndown and        for weed control in crops that are genetically modified to        resist its effects,    -   Hydroxybenzonitriles e.g. bromoxynil,    -   Imidazolinones e.g. fenamidone, imazapic, imazamox, imazapic,        imazapyr, imazaquin,    -   Isoxazolidinones e.g. clomazone    -   Paraquat as bypyridylium,    -   Phenyl carbamates e.g. desmedipham, phenmedipham,    -   Phenylpyrazoles e.g. pyraflufen-ethyl    -   Phenylpyrazolines e.g. pinoxaden,    -   Pyridinecarboxylic acids or synthetic auxins e.g. picloram,        clopyralid, and triclopyr,    -   Pyrimidinyloxybenzoics e.g. bispyrtbac-sodium    -   Sulfonyureas e.g. amidosulfuron, azimsulfuron,        bensulfuron-methyl, chlorsulfuron, flazasulfuron, foramsulfuron,        flupyrsulfuron-methyl-sodium, nicosulfuron, rimsulfuron,        sulfosulfuron, tribenuron-methyl, trifloxysurlfuron-sodium,        triflusulfuron, tritosulfuron,    -   Triazolopyrimidines e.g. penoxsulam, metosulam, florasulam,    -   Triketones e.g. mesotriones, sulcotrione,    -   Ureas e.g. diuron, linuron,    -   Phenoxycarboxylic acids such as 2,4-D, MCPA, MCPB, mecoprops,    -   Triazines such as atrazine, simazine, terbuthylazine,        and their mixtures.

d) Insecticides

An insecticide is a pesticide used against insects in all developmentalforms. They include ovicides and larvicides used against the eggs andlarvae of insects. Insecticides are used in agriculture, medicine,industry and the household. In the following, suitable chemical classesand examples of insecticides are mentioned:

-   -   Abamectin, emamectin,    -   Anthranilic diamides such as rynaxypyr    -   Synthetic auxins Duch as avermectin,    -   Amidines such as amitraz,    -   Anthranilic diamide Duch as rynaxypyr,    -   Carbamates such as aldicarb, carbofuran, carbaryl, methomyl,        2-(1-methylpropyl)phenyl methylcarbamate,    -   Chlorinated insecticides such as, for example, Camphechlor, DDT,        Hexachlorocyclohexane, gamma-Hexachlorocyclohexane,        Methoxychlor, Pentachlorophenol, TDE, Aldrin, Chlordane,        Chlordecone, Dieldrin, Endosulfan, Endrin, Heptachlor, Mirex,    -   Juvenile hormone mimics such as pyriproxyfen,    -   Neonicotinoids such as imidacloprid, clothianidin, thiacloprid,        thiamethoxam,    -   Organophosphorus compounds such as acephate, azinphos-methyl,        bensulide, chlorethoxyfos, chlorpyrifos, chlorpyriphos-methyl,        diazinon, dichlorvos (DDVP), dicrotophos, dimethoate,        disulfoton, dthoprop, fenamiphos, fenitrothion, fenthion,        fosthiazate, malathion, methamidophos, methidathion,        methyl-parathion, mevinphos, naled, omethoate,        oxydemeton-methyl, parathion, phorate, phosalone, phosmet,        phostebupirim, pirimiphos-methyl, profenofos, terbufos,        tetrachlorvinphos, tribufos, trichlorfon,    -   Oxadiazines such as indoxacarb,    -   Plant toxin derived compounds such as derris (rotenone),        pyrethrum, neem (azadirachtin), nicotine, caffeine,    -   Pheromones such cuellure, methyl eugenol,    -   Pyrethroids such as, for example, allethrin, bifenthrin,        deltamethrin, permethrin, resmethrin, sumithrin, tetramethrin,        tralomethrin, transfluthrin,    -   Selective feeding blockers such as flonicamid, pymetrozine,    -   Spinosyns e.g. spinosad        and their mixtures.

e) Plant Growth Regulators

Plant hormones (also known as phytohormones) are chemicals that regulateplant growth. Plant hormones are signal molecules produced within theplant, and occur in extremely low concentrations. Hormones regulatecellular processes in targeted cells locally and when moved to otherlocations, in other locations of the plant. Plants, unlike animals, lackglands that produce and secrete hormones. Plant hormones shape theplant, affecting seed growth, time of flowering, the sex of flowers,senescence of leaves and fruits. They affect which tissues grow upwardand which grow downward, leaf formation and stem growth, fruitdevelopment and ripening, plant longevity and even plant death. Hormonesare vital to plant growth and lacking them, plants would be mostly amass of undifferentiated cells. In the following, suitable plant growthregulators are mentioned:

-   -   Aviglycine,    -   Cyanamide,    -   Gibberellins such gibberellic acid,    -   Quaternary ammoniums such as chlormequat chloride, mepiquat        chloride,    -   Ethylene generators such ethephone,

f) Rodenticides

Rodenticides are a category of pest control chemicals intended to killrodents. Rodents are difficult to kill with poisons because theirfeeding habits reflect their place as scavengers. They would eat a smallbit of something and wait, and if they do not get sick, they wouldcontinue eating. An effective rodenticide must be tasteless and odorlessin lethal concentrations, and have a delayed effect. In the following,examples for suitable rodenticides are given:

Anticoagulants are defined as chronic (death occurs after 1-2 weeks postingestion of the lethal dose, rarely sooner), single-dose (secondgeneration) or multiple dose (first generation) cumulative rodenticides.Fatal internal bleeding is caused by lethal dose of anticoagulants suchas brodifacoum, coumatetralyl or warfarin. These substances in effectivedoses are antivitamins K, blocking the enzymes K₁-2,3-epoxide-reductase(this enzyme is preferentially blocked by4-hydroxycoumarin/4-hydroxythiacoumarin derivatives) andK₁-quinone-reductase (this enzyme is preferentially blocked byindandione derivatives), depriving the organism of its source of activevitamin K₁. This leads to a disruption of the vitamin K cycle, resultingin an inability of production of essential blood-clotting factors(mainly coagulation factors II (prothrombin), VII (proconvertin), IX(Christmas factor) and X (Stuart factor)). In addition to this specificmetabolic disruption, toxic doses of4-hydroxycoumarin/4-hydroxythiacoumarin and indandione anticoagulantsare causing damage to tiny blood vessels (capillaries), increasing theirpermeability, causing diffuse internal bleedings (haemorrhagias). Theseeffects are gradual; they develop in the course of days and are notaccompanied by any nociceptive perceptions, such as pain or agony. Inthe final phase of intoxication the exhausted rodent collapses inhypovolemic circulatory shock or severe anemia and dies calmly.Rodenticidal anticoagulants are either first generation agents(4-hydroxycoumarin type: warfarin, coumatetralyl; indandione type:pindone, diphacinone, chlorophacinone), generally requiring higherconcentrations (usually between 0.005 and 0.1%), consecutive intake overdays in order to accumulate the lethal dose, poor active or inactiveafter single feeding and less toxic than second generation agents, whichare derivatives of 4-hydroxycoumarin (difenacoum, brodifacoum,bromadiolone and flocoumafen) or 4-hydroxy-1-benzothiin-2-one(4-hydroxy-1-thiacoumarin, sometimes incorrectly referred to as4-hydroxy-1-thiocoumarin, for reason see heterocyclic compounds), namelydifethialone. Second generation agents are far more toxic than firstgeneration agents, they are generally applied in lower concentrations inbaits (usually in the order of 0.001-0.005%), and are lethal aftersingle ingestion of bait and are effective also against strains ofrodents that have become resistant against first generationanticoagulants; thus the second generation anticoagulants are sometimesreferred to as “superwarfarins”. Sometimes, anticoagulant rodenticidesare potentiated by an antibiotic, most commonly by sulfaquinoxaline. Theaim of this association (e.g. warfarin 0.05%+sulfaquinoxaline 0.02%, ordifenacoum 0.005%+sulfaquinoxaline 0.02% etc.) is that theantibiotic/bacteriostatic agent suppresses intestinal/gut symbioticmicroflora that represents a source of vitamin K. Thus the symbioticbacteria are killed or their metabolism is impaired and the productionof vitamin K by them is diminuted, an effect which logically contributesto the action of anticoagulants. Antibiotic agents other thansulfaquinoxaline may be used, for example co-trimoxazole, tetracycline,neomycin or metronidazole. A further synergism used in rodenticidalbaits is that of an association of an anticoagulant with a compound withvitamin D-activity, i.e. cholecalciferol or ergocalciferol (see below).A typical formula used is, e.g., warfarin 0.025-0.05%+cholecalciferol0.01%. In some countries there are even fixed three-componentrodenticides, i.e. anticoagulant+antibiotic+vitamin D, e.g. difenacoum0.005%+sulfaquinoxaline 0.02%+cholecalciferol 0.01%. Associations of asecond-generation anticoagulant with an antibiotic and/or vitamin D areconsidered to be effective even against the most resistant strains ofrodents, though some second generation anticoagulants (namelybrodifacoum and difethialone), in bait concentrations of 0.0025-0.005%are so toxic that no known resistant strain of rodents exists and evenrodents resistant against any other derivatives are reliablyexterminated by application of these most toxic anticoagulants.

Vitamin K₁ has been suggested and successfully used as an antidote forpets or humans, which/who were either accidentally or intentionally(poison assaults on pets, suicidal attempts) exposed to anticoagulantpoisons. In addition, since some of these poisons act by inhibitingliver functions and in progressed stages of poisoning, severalblood-clotting factors as well as the whole volume of circulating bloodlacks, a blood transfusion (optionally with the clotting factorspresent) can save a person's life who inadvertently takes them, which isan advantage over some older poisons.

Metal phosphides have been used as a means of killing rodents and areconsidered single-dose fast acting rodenticides (death occurs commonlywithin 1-3 days after single bait ingestion). A bait consisting of foodand a phosphide (usually zinc phosphide) is left where the rodents caneat it. The acid in the digestive system of the rodent reacts with thephosphide to generate the toxic phosphine gas. This method of vermincontrol has possible use in places where rodents are resistant to someof the anticoagulants, particularly for control of house and field mice;zinc phosphide baits are also cheaper than most second-generationanticoagulants, so that sometimes, in cases of large infestation byrodents, their population is initially reduced by copious amounts ofzinc phosphide bait applied, and the rest of the population thatsurvived the initial fast-acting poison is then eradicated by prolongedfeeding on anticoagulant bait. Inversely, the individual rodents thatsurvived anticoagulant bait poisoning (rest population) can beeradicated by pre-baiting them with nontoxic bait for a week or two(this is important to overcome bait shyness, and to get rodents used tofeeding in specific areas by offering specific food, especially wheneradicating rats) and subsequently applying poisoned bait of the samesort as used for pre-baiting until all consumption of the bait ceases(usually within 2-4 days). These methods of alternating rodenticideswith different modes of action provides a factual or an almost 100%eradication of the rodent population in the area if theacceptance/palatability of bait is good (i.e., rodents readily feed onit).

Phosphides are rather fast acting rat poisons, resulting in that therats are dying usually in open areas instead of the affected buildings.Typical examples are aluminum phosphide (fumigant only), calciumphosphide (fumigant only), magnesium phosphide (fumigant only) and zincphosphide (in baits). Zinc phosphide is typically added to rodent baitsin amounts of around 0.75-2%. The baits have a strong, pungentgarlic-like odor characteristic for phosphine liberated by hydrolysis.The odor attracts (or, at least, does not repulse) rodents, but has arepulsive effect on other mammals; birds, however (notably wildturkeys), are not sensitive to the smell and feed on the bait thusbecoming collateral damage.

Hypercalcemia. Calciferols (vitamins D), cholecalciferol (vitamin D₃)and ergocalciferol (vitamin D₂) are used as rodenticides, which aretoxic to rodents for the same reason that they are beneficial tomammals: they are affecting calcium and phosphate homeostasis in thebody. Vitamins D are essential in minute quantities (few IUs perkilogram body weight daily, which is only a fraction of a milligram),and like most fat soluble vitamins they are toxic in larger doses asthey readily result in the so-called hypervitaminosis, which is, simplysaid, poisoning by the vitamin. If the poisoning is severe enough (thatis, if the dose of the toxicant is high enough), it eventually leads todeath. In rodents consuming the rodenticidal bait it causeshypercalcemia by raising the calcium level, mainly by increasing calciumabsorption from food, mobilising bone-matrix-fixed calcium into ionisedform (mainly monohydrogencarbonate calcium cation, partially bound toplasma proteins, [CaHCO₃]⁺), which circulates dissolved in the bloodplasma, and after ingestion of a lethal dose the free calcium levels areraised sufficiently so that blood vessels, kidneys, the stomach wall andlungs are mineralised/calcificated (formation of calcificates, crystalsof calcium salts/complexes in the tissues thus damaging them), leadingfurther to heart problems (myocard is sensitive to variations of freecalcium levels that are affecting both myocardial contractibility andexcitation propagation between atrias and ventriculas) and bleeding (dueto capillary damage) and possibly kidney failure. It is considered to besingle-dose, or cumulative (depending on concentration used; the common0.075% bait concentration is lethal to most rodents after a singleintake of larger portions of the bait), sub-chronic (death occurringusually within days to one week after ingestion of the bait). Appliedconcentrations are 0.075% cholecalciferol and 0.1% ergocalciferol whenused alone. There is an important feature of calciferols toxicologywhich is that they are synergistic with anticoagulant toxicants. Thismeans that mixtures of anticoagulants and calciferols in the same baitare more toxic than the sum of toxicities of the anticoagulant and thecalciferol in the bait so that a massive hypercalcemic effect can beachieved by substantially lower calciferol content in the bait andvice-versa. More pronounced anticoagulant/hemorrhagic effects areobserved if calciferol is present. This synergism is mostly used inbaits low in calciferol because effective concentrations of calciferolsare more expensive than effective concentrations of most anticoagulants.The historically very first application of a calciferol in rodenticidalbait was, in fact, the Sorex product Sorexa® D (with a different formulathan today's Sorexa® D) back in the early 1970's, containing warfarin0.025%+ergocalciferol 0.1%. Today, Sorexa® CD contains a 0.0025%difenacoum+0.075% cholecalciferol combination. Numerous other brandproducts containing either calciferols 0.075-0.1% (e.g. Quintox®,containing 0.075% cholecalciferol) alone, or a combination of calciferol0.01-0.075% with an anticoagulant are marketed.

g) Miticides, Moluscicides and Nematicides

Miticides are pesticides that kill mites. Antibiotic miticides,carbamate miticides, formamidine miticides, mite growth regulators,organochlorine, permethrin and organophosphate miticides all belong tothis category. Molluscicides are pesticides used to control mollusks,such as moths, slugs and snails. These substances include metaldehyde,methiocarb and aluminium sulfate. A nematicide is a type of chemicalpesticide used to kill parasitic nematodes (a phylum of worm). Anematicide is obtained from a neem tree's seed cake; which is theresidue of neem seeds after oil extraction. The neem tree is known byseveral names in the world but was first cultivated in India sinceancient times.

h) Antimicrobials

In the following examples, antimicrobials suitable for agrochemicalcompositions according to the present invention are given. Bactericidaldisinfectants mostly used are those applying

-   -   active chlorine (i.e., hypochlorites, chloramines,        dichloroisocyanurate and trichloroisocyanurate, wet chlorine,        chlorine dioxide, etc.),    -   active oxygen (peroxides such as peracetic acid, potassium        persulfate, sodium perborate, sodium percarbonate and urea        perhydrate),    -   iodine (iodpovidone (povidone-iodine, Betadine), Lugol's        solution, iodine tincture, iodinated nonionic surfactants),    -   concentrated alcohols (mainly ethanol, 1-propanol, called also        n-propanol and 2-propanol, called isopropanol and mixtures        thereof; further, 2-phenoxyethanol and l- and 2-phenoxypropanols        are used),    -   phenolic substances (such as phenol (also called “carbolic        acid”), cresols (called “Lysole” in combination with liquid        potassium soaps), halogenated (chlorinated, brominated) phenols,        such as hexachlorophene, triclosan, trichlorophenol,        tribromophenol, pentachlorophenol, Dibromol and salts thereof),    -   cationic surfactants such as some quaternary ammonium cations        (such as benzalkonium chloride, cetyl trimethylammonium bromide        or chloride, didecyldimethylammonium chloride, cetylpyridinium        chloride, benzethonium chloride) and others, non-quarternary        compounds such as chlorhexidine, glucoprotamine, octenidine        dihydrochloride, etc.),    -   strong oxidizers such as ozone and permanganate solutions;    -   heavy metals and their salts such as colloidal silver, silver        nitrate, mercury chloride, phenylmercury salts, copper sulfate,        copper oxide-chloride etc. Heavy metals and their salts are the        most toxic and environmentally hazardous bactericides and,        therefore, their use is strongly suppressed or forbidden;        further, also    -   properly concentrated strong acids (phosphoric, nitric,        sulfuric, amidosulfuric, toluenesulfonic acids) and    -   alcalis (sodium, potassium, calcium hydroxides) between pH<1        or >13, particularly below elevated temperatures (above 60° C.)        kill bacteria.

As antiseptics (i.e., germicide agents that can be used on human oranimal body, skin, mucoses, wounds and the like), few of the abovementioned disinfectants can be used under proper conditions (mainlyconcentration, pH, temperature and toxicity toward man/animal). Amongthem, important are

-   -   Some properly diluted chlorine preparations (e.g. Daquin's        solution, 0.5% sodium or potassium hypochlorite solution,        pH-adjusted to pH 7-8, or 0.5-1% solution of sodium        benzenesulfochloramide (chloramine B)), some    -   iodine preparations such as iodopovidone in various galenics        (ointments, solutions, wound plasters), in the past also Lugol's        solution,    -   peroxides as urea perhydrate solutions and pH-buffered 0.1-0.25%        peracetic acid solutions,    -   alcohols with or without antiseptic additives, used mainly for        skin antisepsis,    -   weak organic acids such as sorbic acid, benzoic acid, lactic        acid and salicylic acid    -   some phenolic compounds such as hexachlorophene, triclosan and        Dibromol, and    -   cation-active compounds such as 0.05-0.5% benzalkonium, 0.5-4%        chlorhexidine, 0.1-2% octenidine solutions.

Bactericidal antibiotics kill bacteria; bacteriostatic antibiotics onlyslow down their growth or reproduction. Penicillin is a bactericide, asare cephalosporins. Aminoglycosidic antibiotics can act in both abactericidic manner (by disrupting cell wall precursor leading to lysis)or bacteriostatic manner (by connecting to 30 s ribosomal subunit andreducing translation fidelity leading to inaccurate protein synthesis).Other bactericidal antibiotics according to the present inventioninclude the fluoroquinolones, nitrofurans, vancomycin, monobactams,co-trimoxazole, and metronidazole Preferred actives are those withsystemic or partially systemic mode of action such as for exampleazoxystrobin.

Overall preferred are biocides selected either

-   -   (i) from the group consisting of azoles, strobilurines, diphenyl        ethers, anilides, organophosphates, synthetic pyrethroids,        neonicotinoids, oxadiazines, benzoylureas, phenyl carbamates,        chloroacetamides, triketones, pyridinecarboxylic acids,        cyclohexanedione oximes, phenylpyrazoles, glyphosate and its        salts, and their mixtures, or    -   (ii) from the group consisting of oxyfluorofen, propanil,        chlorpyrifos, bifenthrin, deltamethrin, azoxystrobin,        krexoxim-methyl, lambda-cyhalothrin, novaluron, lufenuron,        imidacloprid, thiacloprid, indoxacarb, oxyfluorfen, fluoroxypyr        and its esters, phenmedipham, desmedipham, acetochlor,        tebuconazole, epoxiconazole, propiconazole, fenbuconazole,        triademenol, fipronil, and their mixtures.

Oil Components or Co-Solvents

Suitable oil components or co-solvents (component c) are, for example,Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to10, carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear orbranched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylicacids with linear or branched C₆-C₂₂-fatty alcohols, such as, forexample, myristyl myristate, myristyl palmitate, myristyl stearate,myristyl isostearate, myristyl oleate, myristyl behenate, myristylerucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetylisostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearylmyristate, stearyl palmitate, stearyl stearate, stearyl isostearate,stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate,isostearyl palmitate, isostearyl stearate, isostearyl isostearate,isostearyl oleate, isostearyl behenate, isostearyl oleate, oleylmyristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyloleate, oleyl behenate, oleyl erucate, behenyl myristate, behenylpalmitate, behenyl stearate, behenyl isostearate, behenyl oleate,behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate,erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate anderucyl erucate. Also suitable are esters of linear C₆-C₂₂-fatty acidswith branched alcohols, in particular 2-ethylhexanol, esters ofC₁₈-C₃₈-alkylhydroxy carboxylic acids with linear or branchedC₆-C₂₂-fatty alcohols, in particular Dioctyl Malate, esters of linearand/or branched fatty acids with polyhydric alcohols (such as, forexample, propylene glycol, dimerdiol or trimertriol) and/or Guerbetalcohols, triglycerides based on C₆-C₁₀-fatty acids, liquidmono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters ofC₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylicacids, in particular benzoic acid, esters of C₂-C₁₂-dicarboxylic acidswith linear or branched alcohols having 1 to 22 carbon atoms (Cetiol® B)or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups,vegetable oils, branched primary alcohols, substituted cyclohexanes,linear and branched C₆-C₂₂-fatty alcohol carbonates, such as, forexample, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based onfatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, estersof benzoic acid with linear and/or branched C₆-C₂₂-alcohols (e.g.Cetiol® AB), linear or branched, symmetrical or asymmetrical dialkylethers having 6 to 22 carbon atoms per alkyl group, such as, forexample, dicaprylyl ether (Cetiol® OE), ring-opening products ofepoxidized fatty acid esters with polyols, silicone oils(cyclomethicones, silicone methicone grades, etc.), aliphatic ornaphthenic hydrocarbons, such as, for example, squalane, squalene ordialkylcyclohexanes, and/or mineral oils.

The preferred oil components or co-solvents show an ester structure.Particularly preferred are adipates (Cetiol® B, Agnique® DiME 6),lactates, methyl esters of vegetable oils (Agnique ME 18RD-F, Agnique®ME 12C-F), alkyl esters (Agnique® Ae 3-2EH=2-EthylHexyl Lactate)—allproducts available in the market from Cognis GmbH, Dusseldorf.

Emulsifiers

Suitable emulsifiers (component d) include non-ionic and anionicsurfactants and their mixtures. Non-ionic surfactants include forexample:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0        to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols, onto        C₁₂₋₂₂ fatty acids and onto alkyl phenols containing 8 to 15        carbon atoms in the alkyl group;    -   C_(12/18) fatty acid monoesters and diesters of addition        products of 1 to 30 mol ethylene oxide onto glycerol;    -   glycerol mono- and diesters and sorbitan mono- and diesters of        saturated and unsaturated fatty acids containing 6 to 22 carbon        atoms and ethylene oxide addition products thereof;    -   addition products of 15 to 60 mol ethylene oxide onto castor oil        and/or hydrogenated castor oil;    -   polyol esters and, in particular, polyglycerol esters such as,        for example, polyglycerol polyricinoleate, polyglycerol        poly-12-hydroxystearate or polyglycerol dimerate isostearate.        Mixtures of compounds from several of these classes are also        suitable;    -   addition products of 2 to 15 mol ethylene oxide onto castor oil        and/or hydrogenated castor oil;    -   partial esters based on linear, branched, unsaturated or        saturated C_(6/22) fatty acids, ricinoleic acid and        12-hydroxystearic acid and glycerol, polyglycerol,        pentaerythritol, dipentaerythritol, sugar alcohols (for example        sorbitol), alkyl glucosides (for example methyl glucoside, butyl        glucoside, lauryl glucoside) and polyglucosides (for example        cellulose);    -   mono-, di and trialkyl phosphates and mono-, di- and/or        tri-PEG-alkyl phosphates and salts thereof;    -   wool wax alcohols;    -   polysiloxane/polyalkyl polyether copolymers and corresponding        derivatives;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol and/or mixed esters of C₆₋₂₂ fatty acids, methyl        glucose and polyols, preferably glycerol or polyglycerol,    -   polyalkylene glycols and

The addition products of ethylene oxide and/or propylene oxide ontofatty alcohols, fatty acids, alkylphenols, glycerol mono- and diestersand sorbitan mono- and diesters of fatty acids or onto castor oil areknown commercially available products. They are homologue mixtures ofwhich the average degree of alkoxylation corresponds to the ratiobetween the quantities of ethylene oxide and/or propylene oxide andsubstrate with which the addition reaction is carried out. C_(12/18)fatty acid monoesters and diesters of addition products of ethyleneoxide onto glycerol are known as lipid layer enhancers for cosmeticformulations. The preferred emulsifiers are described in more detail asfollows:

a) Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acidmonoglyceride, hydroxyystearic acid diglyceride, isostearic acidmonoglyceride, isostearic acid diglyceride, oleic acid monoglyceride,oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic aciddiglyceride, linoleic acid monoglyceride, linoleic acid diglyceride,linolenic acid monoglyceride, linolenic acid diglyceride, erucic acidmonoglyceride, erucic acid diglyceride, tartaric acid monoglyceride,tartaric acid diglyceride, citric acid monoglyceride, citric aciddiglyceride, malic acid monoglyceride, malic acid diglyceride andtechnical mixtures thereof which may still contain small quantities oftriglyceride from the production process. Addition products of 1 to 30,and preferably 5 to 10, mol ethylene oxide onto the partial glyceridesmentioned are also suitable.

b) Sorbitan Esters

Suitable sorbitan esters are sorbitan monoisostearate, sorbitansesquiisostearate, sorbitan diisostearate, sorbitan triisostearate,sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitantrioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitandierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate,sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitandihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate,sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate,sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate,sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof.Addition products of 1 to 30, and preferably 5 to 10, mol ethylene oxideonto the sorbitan esters mentioned are also suitable.

c) Alk(en)yl Oligoglycosides

The alkyl or alkenyl oligoglycosides representing also preferredemulsifiers may be derived from aldoses or ketoses containing 5 or 6carbon atoms, preferably glucose. Accordingly, the preferred alkyland/or alkenyl oligoglycosides are alkyl or alkenyl oligoglucosides.These materials are also known generically as “alkyl polyglycosides”(APG). The alk(en)yl oligoglycosides according to the inventioncorrespond to formula (IV):

R⁴O[G]_(p)  (IV)

wherein R⁴ is an alkyl or alkenyl radical having from 6 to 22 carbonatoms, G is a sugar unit having 5 or 6 carbon atoms and p is a numberfrom 1 to 10. The index p in general formula (II) indicates the degreeof oligomerisation (DP degree), i.e. the distribution of mono- andoligoglycosides, and is a number of 1 to 10. Whereas p in a givencompound must always be an integer and, above all, may assume a value of1 to 6, the value p for a certain alkyl oligoglycoside is ananalytically determined calculated quantity which is mostly a brokennumber. Alk(en)yl oligoglycosides having an average degree ofoligomerisation p of 1.1 to 3.0 are preferably used. Alk(en)yloligoglycosides having a degree of oligomerisation below 1.7 and, moreparticularly, between 1.2 and 1.4 are preferred from the applicationalpoint of view. The alkyl or alkenyl radical R⁵ may be derived fromprimary alcohols containing 4 to 22 and preferably 8 to 16 carbon atoms.Typical examples are butanol, caproic alcohol, caprylic alcohol, capricalcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetylalcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleylalcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol,gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixturesthereof such as are formed, for example, in the hydrogenation oftechnical fatty acid methyl esters or in the hydrogenation of aldehydesfrom Roelen's oxo synthesis. Alkyl oligoglucosides based on hydrogenatedC₈-C₁₆ coconut oil alcohol having a DP of 1 to 3 are preferred. Alsosuitable are alkoxylation products of alkyl oligoglucosides, for exampleadducts of 1 to 10 moles ethylene oxide and/or 1 to 5 moles propyleneoxide to C₈-C₁₀ or C₁₂-C₁₈ alkyl oligoglucoside having a DP between 1.2and 1.4.

d) Alkoxylated Vegetable Oils

Suitable emulsifiers are castor oil, rape seed oil, soy been oilethoxylated with 3 to 80 moles ethylene oxide (Agnique® CSO 35, Agnique®SBO 10, Agnique® SBO 60))

e) Alkoxylated Copolymers

Typical copolymers are ethoxylated and propoxylated block and/or randompolymers of C₂-C₂₂ linear or branched alcohols.

f) Anionic Emulsifiers

Typical anionic emulsifiers encompass alkylbenzene sulfonic acids andtheir salts, as for example calcium dodecylbenzene sulfonate dissolvedin isobutanol (Agnique® ABS 65C) or 2-ethylhexanol (Agnique® ABS60C-EH), dialkyl sulfosuccinates, as for example di-2-ethylhexylsulfosuccinate or dioctyl sulfosuccinate, and polyacrylates having amolar weight of from 1,000 to 50,000.

g) Miscellaneous Emulsifiers

Other suitable emulsifiers are zwitterionic surfactants. Zwitterionicsurfactants are surface-active compounds which contain at least onequaternary ammonium group and at least one carboxylate and one sulfonategroup in the molecule. Particularly suitable zwitterionic surfactantsare the so-called betaines such as the N-alkyl-N,N-dimethyl ammoniumglycinates, for example cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH— or —SO₃H— group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.

Biocide Compositions

Depending on the nature of the biocide the products may show thefollowing compositions:

-   (a) about 0.1% b.w. to about 99% b.w., preferably about 15% b.w. to    about 70% b.w., and most preferably about 20% b.w. to about 45% b.w.    alkoxylated oligoglycerol esters;-   (b) about 1% b.w. to about 99.1% b.w., preferably about 5% b.w. to    about 75% b.w., and most preferably about 15% b.w. to about 40% b.w.    biocides;-   (c) 0 to about 50% b.w., preferably about 5% b.w. to about 30% b.w.    and more preferably about 10% b.w. to about 25% b.w. oil components    or co-solvents and-   (d) 0 to about 15% b.w., and preferably about 5% b.w. to about 10%    b.w., emulsifiers    on the condition that the numbers optionally together with water add    to 100% b.w. The compositions represent concentrates to be diluted    with water to give aqueous formulations for end-users comprising    about 0.5 to about 5, preferably about 0.5 to about 1% of the active    matter represented by the concentrate.

INDUSTRIAL APPLICATION

Another embodiment of the present invention is related to the use ofalkoxylated oligoglycerol esters as adjuvants for biocides. Typically,the esters are used in tank mix or in can formulation in combinationwith a biocide, preferably a fungicide at a dose rate of about 20 andabout 2.000, preferably about 40 to about 500 g/ha adjuvant. As shown bythe following greenhouse examples an optimised product is able to boosta standard biocide formulation in a sub lethal dose from approximately50% control up to more than 95% control.

EXAMPLES Example 1 Synthesis of Diglycerol High Oleic Sunflower FattyAcid Monoester

One mole technical statistic diglycerol+10EO, 1 mole HOSO-ME (High-oleicsunflower fatty acid methyl ester), and 55 g potassium hypophosphite(25% b.w. in methanol) were placed in a flask. The mixture was heated upslowly under stirring to 220° C. The reaction started vigorously at atemperature of about 160 to 180° C. After removing the first majoramount of methanol, the vacuum was slowly reduced to less than 1 mbarand the reaction mixture kept under these conditions for another 3 to 4hours. Once the reaction was completed the product was cooled downwithout any additional purification. 870 g diglycerol sunflower fattyacid monoester were obtained as a clear yellow liquid.

Example 2 Synthesis of Diglycerol Oleic Acid Diester

130 g diglycerol+10EO, 120 g technical oleic acid (Edenor® Ti05, EmeryOleochemicals), and 1.7 g hypophosphorous acid were placed in a flaskand heated up under vigorous stirring to 240° C. The flask was set undernitrogen atmosphere. After the removal of water the ester was cooleddown without any additional purification. 240 g diglycerol oleic aciddiester were obtained as a clear yellowish liquid.

Examples 3 and 4

The following tables 1 and 2 provide storage stable formulationscomprising alkoxylated oligoglycerol esters according to the presentinvention. The composition according to Table 1 was wet milled accordingto standard procedures and showed a particle size (D95) of less than 10μm. Composition 2 was stirred until a stable formulation was obtained.

TABLE 1 Storage stable SC formulation of Azoxystrobin Amount [g] ProductChemical name 250 Azoxystrobin 100 Glycerol 150 Diglycerol esteraccording to Example 2  20 Hydropalat ® 5040 100 Sovermol ® 820 380Water

TABLE 2 EC-formulation of Chlorpyrifos Amount [g] Product Chemical name46 Chlorpyrifos 20 Agnique ® AMD 810 10 Agnique ® ME 890  8 Agnique ®ABS 70 C 16 Diglycerol ester according to Example 2

Examples 5 to 14 Greenhouse Trials

The adjuvant performance of different alkoxylated and non-alkoxylateddiglycerol esters were tested in combination with two commerciallyavailable biocide compositions Amistar® SC 250 (Syngenta, active:strobilurin) and Opus® SC 125 (BASF, active: epoxiconazole) ingreenhouse trials. The adjuvants were added as tank mix adjuvants to thebiocide in amounts of 5% b.w. As test method the Barley Segment Testwith powdery mildew as the pathogenic species was used. The results areshown in Tables 3 and 4. Examples 5 to 14 are according to theinvention, examples C1 to C10 serve for comparison.

TABLE 3 Adjuvant effects on strobilurin Powdery mildew Example Biocide +Adjuvant infection (%) Amistar ® (alone) 59 5 + Diglycerol + 10EO oleyltetraester 9 6 + Diglycerol + 10EO oleyl diester 2 7 + Diglycerol + 10EOoleyl monoester 4 8 + Diglycerol + 10EO linseed monoester 9 9 +Diglycerol + 10EO sunflower monoester 12 C1 + Diglycerol oleyltetraester 29 C2 + Diglycerol oleyl diester 25 C3 + Diglycerol oleylmonoester 21 C4 + Diglycerol linseed monoester 25 C5 + Diglycerolsunflower monoester 31

TABLE 4 Adjuvant effects on epoxiconazole Powdery mildew ExampleBiocide + Adjuvant infection (%) Opus ® (alone) 36 10 + Diglycerol +10EO oleyl tetra ester 19 11 + Diglycerol + 10EO oleyl diester 14 12 +Diglycerol + 10EO oleyl monoester 19 13 + Diglycerol + 10EO linseedmonoester 19 14 + Diglycerol + 10EO sunflower monoester 11 C6 +Diglycerol oleyl tetraester 28 C7 + Diglycerol oleyl diester 25 C8 +Diglycerol oleyl monoester 25 C9 + Diglycerol linseed monoester 24 C10 +Diglycerol sunflower monoester 24

All adjuvants turned out to boost both the strobilurin and theepoxiconazole. However, outstanding results were achieved with aDiglycerolester comprising two oleyl groups. It was also shown that thealkoxylated esters show a superior performance over the non-alkoxylatedspecies known from the state of the art.

1. A biocide composition comprising (a) an alkoxylated oligoglycerolester; (b) a biocide and (c) optionally an oil component or co-solventand/or (d) an emulsifier.
 2. The biocide composition according to claim1, wherein component (a) comprises an alkoxylated oligoglycerol esteraccording to general formula (I)

in which R¹, R² and R³ independently represent either hydrogen or asaturated or unsaturated, linear or branched and optionally hydroxysubstituted acyl radical having 2 to 22 carbon atoms and up to threedouble bonds on condition that at least one of the groups R¹, R² and R³is different from hydrogen, AO stands for an alkylene oxide unitselected from ethylene oxide, propylene oxide, butylene oxide and theirmixtures, n1, n2 and n3 independently mean integers in the range from 1to 100 on condition that the sum (n1+n2+n3) is an integer in the rangeof 10 to 200, and x means an integer in the range of 1.1 to
 10. 3. Thebiocide composition according to claim 1 wherein component (a) comprisesan ethoxylated oligoglycerol ester.
 4. The biocide composition accordingto claim 1, wherein component (a) comprises an alkoxylated oligoglycerolester derived from saturated and unsaturated vegetable fatty acids. 5.The biocide composition according to claim 1, wherein the biocide(component b) is selected from the group consisting of herbicides,fungicides, insecticides, and plant growth regulators.
 6. The biocidecomposition according to claim 1, wherein the biocide (component b) isselected from the group consisting of azoles, strobilurines, diphenylethers, anilides, organophosphates, synthetic pyrethroids,neonicotinoids, oxadiazines, benzoylureas, phenyl carbamates,chloroacetamides, triketones, pyridinecarboxylic acids, cyclohexanedioneoximes, phenylpyrazoles, glyphosate and its salts, and their mixtures.7. The biocide composition according to claim 1, wherein the biocide(component b) is selected from the group consisting of oxyfluorofen,propanil, chlorpyrifos, bifenthrin, deltamethrin, azoxystrobin,krexoxim-methyl, lambda-cyhalothrin, novaluron, lufenuron, imidacloprid,thiacloprid, indoxacarb, oxyfluorfen, fluoroxypyr and its esters,phenmedipham, desmedipham, acetochlor, tebuconazole, epoxiconazole,propiconazole, fenbuconazole, triademenol, fipronil, and their mixtures.8. The biocide composition according to claim 1, comprising an oilcomponent or a co-solvent (component c) that is selected from the groupconsisting of Guerbet alcohols based on fatty alcohols having 6 to 18carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear orbranched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylicacids with linear or branched C₆-C₂₂-fatty alcohols, methyl esters ofC₆-C₂₂ fatty acids, esters of linear C₆-C₂₂-fatty acids with branchedalcohols, esters of C₁₈-C₃₈-alkyl hydroxy carboxylic acids with linearor branched C₆-C₂₂-fatty alcohols, esters of linear and/or branchedfatty acids with polyhydric alcohols and/or Guerbet alcohols,triglycerides based on C₆-C₁₀-fatty acids, liquid mono-/di-/triglyceridemixtures based on C₆-C₁₈-fatty acids, esters of C₆-C₂₂-fatty alcoholsand/or Guerbet alcohols with aromatic carboxylic acids, esters ofC₂-C₁₂-dicarboxylic acids with linear or branched alcohols having 1 to22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6hydroxyl groups, vegetable oils, branched primary alcohols, substitutedcyclohexanes, linear and branched C₆-C₂₂-fatty alcohol carbonates,Guerbet carbonates, based on fatty alcohols having 6 to 18 carbon atoms,esters of monopropylene glycol with C₂-C₁₈ acids and benzoic acid,esters of benzoic acid with linear and/or branched C₆-C₂₂-alcohols,linear or branched, symmetrical or asymmetrical dialkyl ethers having 6to 22 carbon atoms per alkyl group, ring-opening products of epoxidizedfatty acid esters with polyols, silicone oils and/or aliphatic ornaphthenic hydrocarbons, mineral oils and their mixtures.
 9. The biocidecomposition according to claim 1, comprising an oil component thatcomprises an ester structure.
 10. The biocide composition according toclaim 1, comprising an oil component that is selected from the groupconsisting of adipates, lactates, methyl esters of vegetable oils, andalkyl esters.
 11. The biocide composition according to claim 1,comprising an emulsifier (component d) that is selected from the groupconsisting of non-ionic and anionic surfactants or their mixtures. 12.The biocide composition according to claim 1, comprising: (a) 0.1 to 99%b.w. of the alkoxylated oligoglycerol ester, (b) 1 to 99.1% b.w. of thebiocide, (c) 0 to 50% b.w. of the oil component or the co-solvent and(d) 0 to 15% b.w of the emulsifier, on the condition that the numbersadd optionally together with water to 100% b.w.
 13. A method ofpreparing a biocide composition comprising using an alkoxylatedoligoglycerol ester as an adjuvant for the biocide.
 14. The methodaccording to claim 13, comprising using the alkoxylated oligoglycerolester in tank mix or in can formulations.